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Selection of Cu2+ for intercalation from the electronegativity perspective: Improving the cycle stability and rate performance of δ-MnO2 cathode material for aqueous zinc-ion batteries

从电负性角度选择Cu2+插层: 提高水系锌离子电池δ-MnO2正极材料的循环稳定性和倍率性能

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Abstract

Ion intercalation is an effective strategy for improving the cycle stability and rate performance of δ-MnO2 as a cathode material for aqueous zinc-ion batteries. However, in practice, ion selection appears rather arbitrary. In this work, Cu2+ was chosen for δ-MnO2 intercalation because although Cu2+ and Zn2+ have similar diameters, Cu2+ has a slightly higher electronegativity (1.359) than Zn2+ (1.347). Therefore, Cu2+ has a stronger interaction with the MnO2 lattice than Zn2+ and can be stable during the intercalation/deintercalation of Zn2+ and H+. Results showed that the performance of Cu-doped δ-MnO2 (CMO) was greatly improved. Moreover, at the high current density of 2 A g−1, CMO achieved excellent cycle stability with 100% capacity retention after 600 cycles, whereas pristine δ-MnO2 exhibited only 23% capacity retention. When the current density was increased from 0.2 to 2.0 A g−1, the CMO electrode also delivered remarkable rate performance with 72% capacity retention, which was considerably higher than the 32% capacity retention demonstrated by pristine δ-MnO2. Given that Cu2+ has a greater electronegativity than Zn2+, the Cu-O bond formed in CMO acted as a stable structural column and greatly improved the stability of CMO. Cu2+ doping also increased the electronic conductivity and ionic conductivity of CMO and reduced the charge transfer resistance of H+ and Zn2+ at the electrode/electrolyte interface, which improved the rate performance of CMO greatly. This work provides new insights into intercalation strategies to improve the electrochemical performance of batteries.

摘要

离子插层已成为提高δ-MnO2作为水系锌离子电池正极材料的循环稳定性和倍率性能的有效策略, 但在实践中离子的选择似乎相当随意. 本工作选择Cu2+插层δ-MnO2, 因为Cu2+和Zn2+具有相似的直径, 但Cu2+的电负性(1.359)略高于Zn2+(1.347). 因此, Cu2+与MnO2晶格具有更强的相互作用, 并且在Zn2+和H+的嵌入/脱出循环期间可保持稳定. Cu掺杂的δ-MnO2(CMO)生成了Cu–O键, 其电化学性能得到了较大的改善. 在2 A g−1的高电流密度下循环600次后, CMO表现出出色的循环稳定性和100%的容量保持率, 而原始δ-MnO2的容量保持率仅为23%. 当电流密度从0.2增加到2.0 A g−1时, CMO还表现出优异的倍率性能, 容量保持率为72%, 远高于原始δ-MnO2(32%). 由于Cu2+比Zn2+具有更大的电负性, 因此Cu–O键作为稳定的“结构之柱”提高了CMO的循环稳定性. Cu2+掺杂还提高了CMO的电子电导率和离子电导率, 降低了H+和Zn2+在电极/电解质界面的电荷转移电阻, 从而提高了其倍率性能. 这项工作为使用插层策略提高电池电化学性能提供了新的见解.

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Acknowledgements

This work was supported by Gansu Provincial Natural Science Foundation of China (17JR5RA198 and 21JR7RA470), the Cooperation Project of Gansu Academy of Sciences (2020HZ-2), the Fundamental Research Funds for the Central Universities (lzujbky-2018-119, lzujbky-2018-ct08, and lzujbky-2019-it23), and the Key Areas Scientific and Technological Research Projects in Xinjiang Production and Construction Corps (2018AB004), Hubei University of Arts and Science (2020kypytd002), and Xiangyang Science and Technology Research and Development (2020YL09).

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Authors and Affiliations

  1. National & Local Joint Engineering Laboratory for Optical Conversion Materials and Technology, School of Materials & Energy, Lanzhou University, Lanzhou, 730000, China

    Zhenhua Liu  (刘振华), Yanpeng Liu  (刘彦鹏), Yanan Zhang  (张亚男), Xiaoli Liu  (刘晓莉), De Yan  (闫德), Juanjuan Huang  (黄娟娟) & Shanglong Peng  (彭尚龙)

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  1. Zhenhua Liu  (刘振华)
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  2. Yanpeng Liu  (刘彦鹏)
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  3. Yanan Zhang  (张亚男)
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  4. Xiaoli Liu  (刘晓莉)
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  5. De Yan  (闫德)
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  6. Juanjuan Huang  (黄娟娟)
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  7. Shanglong Peng  (彭尚龙)
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Contributions

Author contributions Liu Z and Liu Y designed and engineered the samples; Liu Z and Zhang Y conceived the post-fabrication tuning of random modes; Liu Z and Liu X performed the experiments; Liu Z, Liu Y, Yan D, Huang J, and Peng S contributed to the theoretical analysis. All authors contributed to the general discussion.

Corresponding authors

Correspondence to De Yan  (闫德), Juanjuan Huang  (黄娟娟) or Shanglong Peng  (彭尚龙).

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Conflict of interest The authors declare that they have no conflict of interest.

Supplementary information Supporting data are available in the online version of the paper.

Zhenhua Liu is currently a master student at the School of Materials and Energy, Lanzhou University. Her research interest focuses on aqueous zinc-ion batteries.

Shanglong Peng is a professor and doctoral advisor at Lanzhou University. He received his doctor’s degree from Lanzhou University in 2008. He was employed as an associate professor and professor at Lanzhou University. Currently, he mainly focuses on the relevant theoretical and technological innovations and applications of clean energy materials and devices, such as solar cells, lithium/ sodium-ion batteries, and photovoltaic coupled electrolytic water hydrogen production materials and devices related to hydrogen energy development.

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Selection of Cu2+ for intercalation from the electronegativity perspective: Improving the cycle stability and rate performance of δ-MnO2 cathode material for aqueous zinc-ion batteries

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Liu, Z., Liu, Y., Zhang, Y. et al. Selection of Cu2+ for intercalation from the electronegativity perspective: Improving the cycle stability and rate performance of δ-MnO2 cathode material for aqueous zinc-ion batteries. Sci. China Mater. 66, 531–540 (2023). https://doi.org/10.1007/s40843-022-2179-7

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